AU606682B2 - Water-resistant support material for light sensitive materials - Google Patents

Water-resistant support material for light sensitive materials Download PDF

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Publication number
AU606682B2
AU606682B2 AU15240/88A AU1524088A AU606682B2 AU 606682 B2 AU606682 B2 AU 606682B2 AU 15240/88 A AU15240/88 A AU 15240/88A AU 1524088 A AU1524088 A AU 1524088A AU 606682 B2 AU606682 B2 AU 606682B2
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Prior art keywords
water
ethylene
support material
resistant support
percent
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AU1524088A (en
Inventor
Ralf-Burkhard Dr. Dipl. Chem. Dethlefs
Bernd Dipl.-Ing. Scholz
Wolfram Dipl. Ing. Wysk
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Felex Schoeller Jr and GmbH and Co KG
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Felex Schoeller Jr and GmbH and Co KG
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00Ancillary operations in connection with laminating processes
    • B32B38/0008Electrical discharge treatment, e.g. corona, plasma treatment; wave energy or particle radiation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79Macromolecular coatings or impregnations therefor, e.g. varnishes
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/76Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/795Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/25Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • Y10T428/31895Paper or wood
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • Y10T428/31895Paper or wood
    • Y10T428/31899Addition polymer of hydrocarbon[s] only
    • Y10T428/31902Monoethylenically unsaturated
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31909Next to second addition polymer from unsaturated monomers
    • Y10T428/31913Monoolefin polymer

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Thermal Sciences (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Hybrid Cells (AREA)
  • Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The waterproof base for light-sensitive materials is coated on one or both sides with polyolefin resin, at least the polyolefin resin of the front coating containing a copolymer of ethylene and another alpha -olefin. This copolymer makes it possible to add a high proportion of light-reflecting white pigment to the coating composition.

Description

COMMONWEALTH OF AUSTRALIA Patent Act 1952 606682 COMPLETE S P E C I F I C A T ION
(ORIGINAL)
Application Number Lodged Complete Specification Lodged Accepted Class Int. Class amendments ni d und bc'eilon 49 and is cor ect for printing ii
I,
I
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Published *4 ~e 4* 4 .4 I, 0
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0 0 4.
0 j 4 0 q.
4 0 Priority 15 May 1987 Related Art Name of Applicant Address of Applicant Actual Inventor/s Address for Service FELIX SCHOELLER JR. GMBH CO
KG
Burg Gretesch, D-4500 Osnabruck Feleral Republic of Germany z Ralf-Burkhard Dethlefs Bernd Scholz Wolfram Wysk F.B. RICE CO., Patent Attorneys, 28A Montague Street, BALMAIN 2041.
Complete Specification for the invention entitled: WATER-RESISTANT SUPPORT MATERIAL FOR LIGHT-SENSITIVE MATERIALS The following statement is a full description of this invention including the best method of performing it known to us/rm:- BACKGROUND OF THE INVENTION 1. Field of the Invention The invention relates to a photographic support material with a water-resistant coating of a polyolefin resin.
2. Brief Description of the Background of the Invention Including Prior Art Water-resistant photographic support materials comprise a plastic film or a base paper with synthetic resin coatings applied to preferably both sides, which include polymers, for example pol.yethylene., and which are applied by way of extrusion coating or which comprise an organic lacquer mixture, which is placed on the paper by way of a submersion or spray method and which is dried and hardened or solidified by employing heat or energy-rich f* radiation.
I. e One or several silver halides containing light-sensitive layers are applied on one of the resin layers. In case of light-sensitive layers, it can refer to both black and white as well as colour photographic layers.
The synthetic resin layer (front-side coating) disposed under the light-sensitive layer or, respectively, layers comprises usually a light-reflecting white pigment 25 as well as possibly color pigments, optical brighteners and/or other additives such as antistatic agents, dispersion additives for the white pigment, antioxidants, separating agents, and the like.
The synthetic resin layer, disposed on the paper side opposite to that of the one with the light-sensitive layers (back-side coating), can be pigmented or can be left unpigmented and/or can contain other additives, which result from the use of the laminate as a photographic support material in each case and which, in principle, can correspond to those of the front-side coating.
with additional function layers which can improve, for example, the capability of writing on the material, the antistatic property, the slip properties, the flatness (planarity) or several of these properties.
In order to achieve that a resin coated photographic paper support, after a one-side application of photographic layers, does not exhibit an undesirable curvature (curl,) it is usually provided that the C* .front-side polyethylene layer comprises substantially a low-density polyethylene (LDPE), whereas the back-side 15 polyethylene layer predominantly comprises a high-density .ee. polyethylene (HDPE), compare German Patent Application Laid Open DE-OS 2,028,600.
6***S The coating of a photographic base paper or of a film material with polyolefin coating by way of extrusion via a slot die is a method known in the art. It is also known that, during the extrusion of the polyethylene, certain 'difficulties occur, which can result, owing to the high sensitivity of the photographic process, in perceivable 0 disturbances in photographic layers or even in a uselessness of the support material.
The use of low-density polyethylenes (LDPE), produced by polymerizing ethylene according to the high-pressure method, transfers the disadvantages of insufficient stiffness and hardness of this polyethylene to the photographic paper support, which can be noticed by an insufficient overall stiffness of the final product and, in particular, in case of glossy surfaces, by an increased tendency to sticking in the wound roll.
However, also the use of polyethylene of higher density (HDPE), produced by polymerization of ethylene 4 according the low-pressure method, transfers to the photographic-paper support material disadvantages which are generated by the higher melt viscosity and the crystallinity of the high-density polyethylene or result from the additives added to this polyethylene necessary for purposes of stabilization, if this polyethylene is employed in a front-side coating. These disadvantages include a weak and insufficient adhesion on the paper support and an unsatisfactory planarity of the coated paper. In addition, the low "draw-down" of the high-density polyethylene can be a disadvantage, in particular where thinner coatings are desired.
In order to limit the disadvantages associated with the individual polyethylene types, optimized mixtures of 15 low-density polyethylene and high-density polyethylene are usually employed, US 4 699 874).
It is a joint property of the two polyethylene types S" and of their mixtures that they can only be filled to a limited extend with pigments. It is taught in German Patent Application Laid Open DE-OS 3,411,681 (English language equivalent GB 21 389 64) how much the sharpness of a photographic image depends on the extent of reflection of the impinging light off the white pigments.
Therefore, it is an important goal of all light-sensitive 25 support materials to improve this reflection of the impinging light. This is achieved by employing white *o .pigments with the highest indices of refraction, such as titanium dioxide, and by maintaining as high as possible the content in white pigment in the polyolefin resin with a very good dispersion such that a dense pigment packing is generated and present in the support near the surface.
It has to be avoided in this context to generate pigment agglomerates in the polyolefin resin, since they decrease on the one hand the total light reflection and, on the other hand, they can result in disturbances and interferences during the drawing of the melt film in the extrusion coating, or later during the casting of the resin coated support with light-sensitive emulsions.
In practice of extrusion coating, the pigment concentration in a polyethylene resin coating mixture has been limited hitherto to less than 20 weight-percent and is usually between 10 and 17 weight-percent. This holds both for a pure low-density polyethylene as well as for the described mixtures of low-density polyethylene and high-density polyethylene.
The various problems associated with all'photographic paper support materials coated with polyethylene have resulted in further specific developments. Such 0e..
developments are for example described in the German 15 Patent Application P 3,627,859.9. According to that e g.
patent application, the sum of the associated disadvantages is clearly improved on in several aspects.
However, the results are not satisfactory in that the titanium-dioxide concentration is limited to about 20 percent and that the number of the pigment agglomerates is only slightly decreased.
SUMMARY OF THE INVENTION •i1. Purposes of the Invention It is an object of the present invention to provide a photographic support material coated with a polyolefin resin, which accepts an increased filling degree with pigments and results in a lower number of pigment agglomerates upon use of titanium-dioxide pigment in the front-side coating.
It is another object of the present invention to provide a coating mixture which allows to produce a photographic support material with an improved front-side coating containing a higher pigment-filling degree and a lower number of pigment agglomerates.
It is yet another object of the present invention to bCi( 6 0@
S
S
SS
0 ~i 5555 Si e 5 55 Se S
S
provide a support material coated with polyolefin resin which exhibits an increased light-reflection.
These and other objects and advantages of the present invention will become evident from the description which follows.
2. Brief Description of the Invention A water-resistant support material for light sensitive layers comprises a substantially flat base material. Polyolefin resin i,s coated onto a front side of the base material for forming a coating. The coating on the front side comprises in addition a light-reflecting white pigment on the face of the base material paper or film) to be coated with light-sensitive layers. The polyolefin resin on the front side contains a so-called 15 linear low density polyethylene (LLDPE), a copolymer of ethylene and non-ethylene A,-olefin. The oC olefins are unsaturated aliphatic hydrocarbons having a double bond next to a terminal carbon atom. [Such LLDPE linear low density polyethylenes are known and for example taught in 20 the article "A study of linear low-density polyethylenes: branch content, branch distribution and crystallinity" by C. France et al. in Polymer, 1987, Vol 28. April, pages 710-712.] Polyolefin resin can further be coated onto the 25 opposite side of the base material for forming a coating.
This back-side coating can comprise any type of polyolefin. A prefered combination is a mixtufr of HDPE and LDPE, but inclusion of LLDPE is possible.
The base material can be provided by any photographic base paper or by any film base.
The base material can be natural or synthetic paper PlteCics material or a film material.
The light-reflecting white pigment in the front-side coating can be a titanium dioxide. The content of titanium dioxide in the coating material can amount up to -7weight-percent. The coating mass can comprise at least one of the conventional additives selected from the group consisting of matting agents, antistatics, antioxidants, slip additives, lubricants, pigments, coloring agents, optical brighteners, and seperating agents.
The so-called LLDPE is a copolymer consisting or comprising of ethylene and a non-ethylene 4-olefin with a chain-length of 3-18 carbon atoms and preferably 4 to 8 carbon atoms. The content of non-ethylene A-olefin in the copolymer can range to from about 0.1 to 20 molepercent.
Furthermore a premixture composition is disclosed for the production of water-resistant support materials, comprising polyolefin resin and light-reflecting white 15 pigment. The polyolefin component in the premixture is a copolymer of ethylene and non-ethylene Q.-olefin, a **so-called linear low-density polyethylene, LLDPE. The light-reflecting white pigment is intimately mixed with SI the said polyolefin resin. The light-reflecting white pigment preferably is titanium dioxide. The content of titanium oxide in the composition can range from about to 70 weight-percent. Additional additives can be selected from the group consisting of coloring agents, pigments, optical brightenets, matting agents, dispersing agents, slip additives, lubricants, separating agents, S* antistatic agents, antioxidants, and mixtures thereof.
The contents of LLDPE in the premixture composition t. can range from about 10 weight-percent to 100 S" weight-percent of the complete polyolefin resin. The non-ethylene oolefin in the copolymer can comprise C 3 to C 18 carbon atoms and has preferably C 4 to C 8 carbon atoms. The content of non-ethylene t-olefin in the copolymer can range from about 0.1 to 20 mole-percent.
A method for production of a water-resistant support material can comprise melt-extruding a water-resistant
I
-8resin coating material onto a base material. The front-side resin coating material contains white pigment and a copolymer of ethylene and non-ethylene o--olefin, which copolymer is a so-called linear low-density polyethylene, LLDPE.
A base material of paper or film can be coated with the water-resistant resin coating material. The light-reflecting white pigment can be titanium dioxide.
The content of light-reflecting white pigment, e.g.
titanium dioxide, in the coating material can amount up to weight-percent. Light-sensitive coatings can be applied on the pigment-containing resin layer.
According to the invention, the front-side coating '$feeri~ a oro e. kr offI fle--e, .comprises a copolymer of ethylene and at least one 9 her s15 a-olefin. Such copolymers are known in principle as *.eo go so-called linear low-density polyethylene, LLDPE types, and can be produced according to the low-pressure method as well as the high-pressure method.
5S5505 These so-called linear low-density polyethylenes (LLDPE) have, depending on the kind and content in comonomers, a density of 0.880 to 0.960 g/cm 3 The use of these modified polyethylenes with stereospecific molecular structure allows a complete series of improvements. For example, linear low-density polyethylenes exhibit a higher stiffness and crystallinity than the low-density polyethylene and they resemble, with respect to their molecular structure, more to the high-density polyethylene. In addition, the puncture resistance properties as well as the abrasion strength are improved (Plastverarbeiter 33 (1982), 9, pp. 1035-1037, as well as Kunststoffe 73 (1983), 5, pp. 251-254).
However, it was surprisingly found that the addition of linear low-density polyethylene (LLDPE) to the coating mass.,j.whlf. comp.rises substantially polyolefin resin and ti~aniu dioxi.de, allows -a substantially increased pigment A- a -9- 4 *e
I~
4 S be 0 filling and that this pigment filling exhibited even a lesser part in pigment agglomerates. It was further unexpected that there was obtained a stronger adhesion of the coating material according to the present invention to the base paper as compared with a coating material without linear low-density polyethylene under the same conditions.
In particular, the content in pigment agglomerates could be decreased, where the titanium dioxide was processed initially with a linear low-density polyethylene (LLDPE) in a premixture composition with a kneader or a granulating extruder. Such premixtures, where the titanium-dioxide content can amount up to 70 weightpercent, thus represent a particular embodiment of the invention. They can be added with other components to 15 form the corresponding coating materials.
It was further surprising that even highly filled polyolefin-resin melts, containing more than 15 weightpercent titanium dioxide, can be extruded with a predetermined wide-slot die to thinner coating thicknesses than in cases where solely low-density polyethylene, high-density polyethylene, or mixtures of the two were employed. This is advantageous in connection with the higher capability of filling of such polyethylene mixtures because it is thereby possible to apply thinner 25 polyethylene layers on the front side without decreasing the reflection properties. In addition, the back-side coating can be reduced in its thickness where a thinner front-side coating is applied. Lower layer thicknesses allow, however, in case of a predetermined overall thickness of the coated paper, to employ a larger thickness of the paper base, which can be noticed in a marked and desired increase in the stiffness of the final prcduct as well as in the lower production costs.
Preferably the extrusion coating is furnished with a slot die, a flat sheet die or a T-die, which has been taught i' B S S 10 early in U.S. patent 3,411,908.
I The novel features which are considered as i characteristics for the invention are set forth in the appended claims. The invention itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will be best understood from the following description of specific embodiments when read in connection with the accompanying i drawing.
DESCRIPTION OF INVENTION AND PREFERRED EMBODIMENT Example 1 i A photographic base paper having a basis weight of 175 g/sq.m was subjected to a Corona pretreatment and than *fe coated on the back-side with 25 g/sq.m of the following 15 mixture: S 70 weight-percent high-density polyethylene, p 0.950 g/cm 3 I 30 weight-percent low-density polyethylene, 0.924 g/cm 3 Immediately thereafter, the front-side was Coronapretreated and coated with 30 g/sq.m of the following mixtures: low density linear low-density Premixture polyethylene polyethylene f density density 0.935 g/cm 3 0.924 g/cm 3 polymerized with 1.0 mol-percent octene A B 1 a 64 0 36 0 b 64 0 20 16 c 57.5 6.5 0 36 S' 30 d 24.5 39.5 0 36 Premixture SA 50 weight-percent titanium dioxide, containing 97.5% rutile and stabilized with A1 2 0 3 weight.percent low density polyethylene having a density of 0.924 g/cm 3 SrI 11 B 50 weight-percent titanium dioxide, containing 97.5% rutile and stabilized with A1 2 0 3 weight-percent linear low-density polyethylene having a density of 0.935 g/cm 3 with 1 molepercent octene The premixtures were produced in a granulating extruder at 130 0
C.
The coatings were performed with a tandem-extrusioncoating plant at 310 0 C melting temperature and 120 m/min machine speed on a band width of 120 cm. Tandem extrusion plants have found wide distribution and their principle of operation is described for example in U.S. patent S.o 4,209,584.
Example 2 15 The photographic base paper used in Example 1 was S coated on the back side according to the coating procedure s*e of Example 1.
Then a front-side Corona treatment was performed and immediately thereafter the front side was coated with 30 g/sq.m of the following mixtures: Mixture of Linear low-density Premixture 70 weight*percent low- polyethylene S* density polyethylene density density 0.915 g/cm 3 0,924 g/cm 3 polymetized with 3.1 mole weight-percent high- percent butene density polyethylene density S* 0.950 g/cm 3 A C S. a 70 0 b 52 0 48 c 54 16 d 44 8 48 e 34 0 66 f 45 25 12 Premixture C 50 weight-percent titanium dioxide, containing 97, rutile and stabilized with A1 2 0 3 weight-percent linear low-density polyethylene with a density of 0.915 g/cm 3 with 3.1 mole-percent butene weight-percent low-density polyethylene with a density of 0.924 g/cm 3 The premixture was produced with a laboratory melt extruder at 300 0 C melting temperature and a machine speed of 20 m/min on a 25-cm band width and pelletized.
Example 3 see A photographic base paper having a basis weight of :200 g/sq.m was subjected to a Corona pretreatment and then 15 coated on the back side with 15 g/sq.m. of the following mixture: *60 weight-percent low-density polyethylene with a density of 0.924 g/cm 3 weight-percent linear low-density polyethylene with a density of 0.935 g/cm 3 polymerized with 1.0 mole-percent octene 0U Immediately following to a Corona pretreatment, the *0 front side was coated according to the following table: Application Low-density polyethylene Premixture 25 g/sq.m density 0.924 g/cm 3 D E a 15 64 36 b 12.5 64 36 c 10 64 36 d 15 64 36 e 12.5 64 36 f 10 64 36 The premixtures had the following composition: D 50 weight-percent low-density polyethylene having a density of 0.924 g/cm 3 13 48.5 weight-percent titanium dioxide, containing 97.5% rutile and stabilized with A1 2 0 3 weight-percent ultramarine blue 0.6 weight-percent antioxidant (Tinuvin 770) 0..2 weight-percent metal stearate 0.2 weight-percent cobalt violet E 50 weight-percent linear low-density polyethylene having a density of 0.920 g/cm 3 with 3.2 molepercent octene 48.5 weight-percent titanium dioxide containing 97.5% rutile and stabilized with A1 2 0 3 weight-percent ultramarine blue 06 weight-percent antioxidant (Tinuvin 770) I 15 0.2 weight-percent metal stearate 0.2 weight-percent cobalt violet The premixtures were produced at 130 0 C in a granulating extruder.
All coatings were performed with a tandem-extrusion- I 20 coating plant at 310 0 c melting temperature and 150 m/min machine speed on a material band width of 120 cm.
S9** ExampLe 4 'The photographic base paper of Example 1 was coated on the back side as set forth in Example 1.
I 25 Immediately thereafter a Corona pretreatment was I performed and the front-side was coated with 30 g/sq.m of the following coating mixtures: 8 4 L kL <tj 4 j, 14 low-density Premixture consisting of polyethylene 50 weight-percent titanium dioxide density containing rutile as set forth 0.924 g/cm 3 in Examples 1 3 50 weight-percent linear low-density polyethylene of the following kind (weight-percent) (weight-percent) a 60 40 linear low-density polyethylene with 14.2 mole-percent propene-(l) b 60 40 linear low-density polyethylene with 8.7 mole-percent butene-(1) c 60 40 linear low-den-ity polyethylene with 3.2 mole-percent butene-(1) 15 d 60 40 linear low-density polyethylene with 5.6 mole-percent 4-methylpentene- (1) e 60 40 linear low-density polyethylene with 4.2 mole-percent octene-(1) f 60 40 linear low-density polyethylene with 1.0 mole-percent uctene-(1) g 60 40 linear low-density polyethylene with 0.2 mole-percent hexadecene-(1) h 60 40 low-density polyethylene for S"comparison, premixture A The premixtures were produced in a granulating S. extruder at 130 0 C. The coatings were performed with a 0 melt extruder at 300 0 C melting temperature and 20 m/min machine speed on a band width of 25 cm.
Description of the Test Methods Filtratest 200 g premixture of 50 weight-percent titanium dioxide and 50 weight-percent polyolefin resin were passed in l) i Ato tyrautruder at a melting temperature of 300 0
C
.ff Owl through a preweighed sieve of a mesh width of 25 ,cm.
Thereafter a pure polyolefin resin was extruded through the same sieve until all pigment-containing material had passed the sieve. After calcining of the sieve at 800 0 C, the residue on the sieve was determined gravimetrically and was recalculated to milligrams of residue per 1 kilogram of titanium dioxide.
Level of Agglomerates In a transmitting light, the pigment agglomerates were counted in an area of 1 sq.m. of the coated paper, which pigment agglomerates could be recognized on an illuminating table as dark dots. This is given as number per square meter.
Adhesion of the Film 15 The adhesion of the polyolefin resin film on the front side of the base paper is determined by a pulling off of a 10 mm wide strip in machine direction of the coating.
Grades from 1 to 5 were applied, where the grade 1 denotes a very good adhesion and grade 5 denotes no adhesion.
Test Results TABLE 1 Filtrate test 25 Premixture Mixture Titanium Dioxide (Ti02) mg residue/kg with TiO 2 A low-density polyethylene 87 density 0.924 g/cm 3 30 B linear low-density polyethylene 24 mole-percent octene-(l)) 16 C low-density polyethylene:linear low- 52 density polyethylene mole-percent butene-(1)) 3:2 D low-density polyethylene 93 density 0.924 g/cm 3 E linear low-density polyethylene 31 (3.2 mole-percent octene-(l)) 4a linear low-density polyethylene 19 (14.2 mole-percent propene-(l)) 4b linear low-density polyethylene 21 (8.7 mole-percent butene-(l)) 4c linear low-density polyethylene (3.2 mole-percent butene-(l)) 4d linear low-density polyethylene 15 (5.6 mole-percent hexene-(l)) S4e linear low-density polyethylene 32 (4.2 mole-percent octene-(1)) 4f linear low-density polyethylene 37 (1.0 mole-percent octene-(l)) 4g linear low-density polyethylene 34 (0.2 mole-percent hexadecene-(1)) e i 9 S S S 55 5 S S S I S S S 55 5 S S S S S S S S S S*S S -f S S S S S S S S S S I S 555 S *SS S S S Example TABLE 2 Composition of the Front-Side Coating 4 tarium Low-Density High-Density Linear ioxide Polyethylene Polyethylene Low Density Polyethylene (in weight-percent) Agglomerates (number per sq. m) Film Adhesion (Note) compar.
copr compar compar compar compar 18 18 18 18 15 24 24 33 17.5 17.5 17-.5 17.5 17.5 17.5 57.5 24 .5 64 60.4 43.8 40.4 37 46.5 82 82 82 64 64 64 60 21 15.6 16.2 13 .2 10.2 13.5 0 8 24.5 57.5 0 0 25 22.4 19.8 25 0 0 0 18 18 18 12 9 6 7 13 elevation in 5 7 8 9 13 11 elevation in 6 5 7 3 3 2 1 3 film not evaluated 1 2 2 1 4 4 film not evaluated 3 4 4
-A
Ob.-
W_
0 0 S 4 0 S S S S S S **0
S
S S
S
S S *0 O' s 0 *5 0 0 0 06 Example TABLE 2 (cont'd) Composition of the Front-Side Coating Titanium Low-Density High-Density Linear Dioxide Polyethylene Polyethylene Low Density P0 lye thylen (in weight-percent) Agglomerates Film Adh esi-on (Note) (number per sq. m) 4 b 20 60 20 6 4 c 20 60 20 4 4 d 20 60 20 4 e 20 60 20 6 4 f 20 60 20 7 4 g 20 60 20 8 4h compar. 20 80 0 12
I
19 The results of the filtratest of the premixtures and of the agglomerates level of the produced coatings illustrate that the mixtures according to the invention, employing the linear low-density polyethylene, have a lower tendency to form pigment agglomerates.
The various examples of Example 2 illustrate that layers with higher pigment levels can be produced with linear low-density polyethylene premixtures than hitherto with pigment-containing low-density polyethylene or high-density polyethylene premixtures. Example 2f illustrates that a lower gel-particle level compared to the comparison example 2a can be achieved even if the i linear low-density polyethylene is added directly to the coating mass and not added via a premixture. This 15 improvement is, however, slightly less than in the preferred addition via a premixture.
I a* The examples of Example 3 clearly illustrate that j ir *thinner coatings can be extruded from a melt if the melt icontains linear low-density polyethylene. This holds even J 20 in case of the recited polyolefin resin mixtures containing a relatively high titanium dioxide content.
e.
1 The examples of Example 4 indicate that the illustrated advantages can be achieved with various types of linear low-density polyethylenes.
25 The examples 1, 2 and 3 also illustrate that linear low-density polyethylene in the coating mass improves finally even the adhesion of the front-side coating on the paper.
It will be understood that each of the elements described above, or two or more together, may also find a useful application in other types of support materials differing from the types described above.
While the invention has been illustrated and described as embodied in the context of a water-resistant support material for light-sensitive materials, it is not i] I S, 20 intended to be limited to the details shown, since various modifications and structural changes may be made without departing in any way from the spirit of the present invention.
Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can, by applying current knowledge, readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic or specific aspects of this invention.
What is claimed as new and desired to be protected by Letters Patent is set forth in the appended claims.
S
SS 0 0 00 S@ 0 00 0@ S 550555 S jj ,?rf -*h

Claims (29)

1. A water-resistant support material for light-sensitive materials, comprising a substantially flat base material; polyolefin resin coated onto a front side of the base material for forming a coating, where the coating comprises, on the face of the base material to be coated with light-sensitive layers, in addition a light-reflecting white pigment and, wherein the polyolefin resin on the front-side contains a so-called linear low-density polyethylene (LLDPE), and wherein the LLDPE is a copolymer of ethylene and a non-ethylene O-olefin.
2. The water-resistant support material according to claim 1 further comprising polyolefin resin coated onto a back side of the core material for forming a coating, where the coating comprises to at least about 10 weight percent a copolymer of ethylene and non-ethylene Co-olefin, a so-called linear low density polyethylene LLDPE.
3. The water-resistant support material according to claim 1, wherein the base material is a paper material.
4. The water-resistant support material according to claim 1, wherein the base material is affilm material.
The water-resistant support material according to claim 1, wherein the light-reflecting white pigment is a titanium dioxide.
6. The water-resistant support material according to claim 5, wherein the content of titanium dioxide in the coating material amounts up to 40 weight-percent.
7. The water-resistant support material according to claim 1, wherein the coating mass comprises at least one of the conventional additives selected from the group consisting of matting agents, antistatics, antioxidants, slip additives, lubricants, pigments, coloring agents, optical brighteners, and separating agents or mixtures I ii -22 thereof.
8. The water-resistant support material according to claim 1, wherein the non-ethylene 4-olefin in the copolymer comprises C 3 to C 1 8 carbon atoms.
9. The water-resistant support material according to claim 8, wherein the non-ethylene a--olefin in the copolymer comprises C 4 to C 8 carbon atoms.
The water-resistant support material according to claim 1, wherein the content of non-ethylene a-olefin in the copolymer amounts to from about 0.1 to 20 mole-percent.
11. A premixture composition for the production of water-resistant support materials coated with polyolefin resin for light-sensitive materials of polyolefin resin and light-reflecting white pigment comprising oi a polyolefin resin formed as a copolymer of ethylene and a non-ethylene a-olefin, a so-called linear low-density polyethylene, LLDPE; and a light-reflecting white pigment intimately mixed with the said polyolefin resin.
12. The composition according to claim 11, wherein the light-reflecting white pigment in titanium dioxide. o
13. The composition according to claim 12, wherein the conteit of titanium oxide in the composition amounts to I *i from about 10 to 70 weight-percent.
14. The composition according to claim 11, further comprising an additive selected from the group consisting of coloring agents, pigments, optical brighteners, delustering agents, dispersing agents, slip additives, lubricants, separating agents, antistatic agents, antioxidants, or mixtures thereof.
The composition according to claim 11, wherein the contents of the copolymer of ethylene and non-ethylene a -olefin amounts to from about 10 weight-percent to 100 weight-percent of the complete polyolefin resin.
16. The composition according to claim 11, wherein the 23 non-ethylene 5C-olefin in the copolymer comprises C 3 to C 18 carbon atoms.
17. The composition according to claim 11, wherein the non-ethylene c-olefin in the copolymer comprises C 4 to C 8 carbon atoms.
18. The composition according to claim 11, wherein the content of non-ethylene a-olefin in the copolymer amounts to from about 0.1 to 20 mole-percent.
19. A method for production of a water-resistant support material comprising melt-extruding a water-resistant coating material onto a 0* I base material, where the coating material comprises a so-called LLDPE, which is a copolymer of ethylene and Snon-ethylene &-olefin and a light reflective white pigment.
The method for production of a water-resistant support material according to claim 19 further comprising supporting light-sensitive materials on the water-resistant coating material.
21. The method for production of a water-resistant support material according to claim 19 further comprising coating a base material of paper with the water-resistant coating material.
22. The method for production of a water-resistant support material according to claim 19, wherein the coating material comprises a member selected from the group consisting of matting agents, antistatics, antioxidants, slip additives, lubricants, coloring agents, pigments, optical brighteners, separating agents, or mixtures thereof.
23. The method for production of a water-resistant support material according to claim 19, wherein the non-ethylene de-olefin in the copolymer comprises C 3 to C18 carbon atoms. 24
24. The method for production of a water-resistant support material according to claim 23, wherein the non- ethylene a-olefin in the copolymer comprises C 4 to C 8 carbon atoms.
The method for production of a water-resistant support material according to claim 19, wherein the content of non-ethylene c--olefin in the copolymer amounts to from about 0.1 to 20 mole-percent.
26. The method for production of a water-resistant support material according to claim 19, wherein the coating material contains titanium dioxide in an amount up 0i, to 40 weight-percent. S
27. A water-resistant support material substantially as *o hereinbefore described with reference to the accompanying So." examples apart from comparative examples.
28. A premixture composition from the production of water-resistant support materials substantially as 000 described with reference to the accompanying examples apart from comparative examples.
29. A method for the production of water-resistant S support material substantially as described with reference i "0 to the accompanying examples apart from comparative i examples. 0000 I DATED this 12 day of November 1990 S FELIX SCHOELLER JR. GMBH j CO. KG Patent Attorneys for the Applicant: F.B. RICE CO.
AU15240/88A 1987-05-15 1988-04-28 Water-resistant support material for light sensitive materials Ceased AU606682B2 (en)

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DE3716269A DE3716269C2 (en) 1987-05-15 1987-05-15 Waterproof substrate for light-sensitive materials
DE3716269 1987-05-15

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US5198330A (en) * 1991-10-11 1993-03-30 Eastman Kodak Company Photographic element with optical brighteners having reduced migration
JP2884281B2 (en) * 1992-07-03 1999-04-19 富士写真フイルム株式会社 Silver halide photographic material
DE4229153C2 (en) * 1992-09-01 1996-01-25 Schoeller Felix Jun Papier Substrate for photographic recording materials
US5318624A (en) * 1992-09-04 1994-06-07 Eastman Kodak Company Process for preparing a dispersion from an agglomerated mixture
JPH06118554A (en) * 1992-10-08 1994-04-28 Fuji Photo Film Co Ltd Substrate for photographic printing paper and its production
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US20030131963A1 (en) * 2002-01-11 2003-07-17 Nowak Michael R. Ream wrap having white or colored poly coating
US20030129431A1 (en) * 1998-10-23 2003-07-10 Michael R. Nowak Composite wrap material
DE202004005474U1 (en) * 2004-04-02 2004-07-08 Felix Schoeller Jr. Foto- Und Spezialpapiere Gmbh & Co. Kg Plastic concentrate for the production of coating compounds
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DE3716269C2 (en) 1993-12-09
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ES2042632T3 (en) 1993-12-16
CN1031963C (en) 1996-06-05
JP2710628B2 (en) 1998-02-10
EP0290852A2 (en) 1988-11-17
US4935298A (en) 1990-06-19
EP0290852A3 (en) 1989-10-04
DE3716269A1 (en) 1988-11-24
DE3881956D1 (en) 1993-07-29
ATE91034T1 (en) 1993-07-15
AU1524088A (en) 1988-11-17
CN88102825A (en) 1988-11-30

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